Catalysts for polyurethane foam polyol premixes containing halogenated olefin blowing agents

ABSTRACT

The invention provides polyurethane and polyisocyanurate foams and methods for the preparation thereof. More particularly, the invention relates to closed-celled, polyurethane and polyisocyanurate foams and methods for their preparation. The foams are characterized by a fine uniform cell structure and little or no foam collapse. The foams are produced with a polyol premix composition which comprises a combination of a hydrohaloolefin blowing agent, a polyol, a silicone surfactant, and a non-amine catalyst used alone or in combination with an amine catalyst.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a division of U.S. application Ser. No.13/400,563, filed Feb. 20, 2012, which application relates to and claimsthe priority benefit of each of U.S. Application 61/445,027, filed Feb.21, 2011 and U.S. Application 61/445,022, filed Feb. 21, 2011, each ofwhich is incorporated herein by reference in its entirety as if fullyset forth below.

Also incorporated herein by reference is U.S. application Ser. No.13/400,559, now U.S. Pat. No. 9,051,442.

FIELD OF THE INVENTION

The present invention pertains to polyurethane and polyisocyanuratefoams, to blowing agents and catalyst systems and methods for thepreparation thereof.

BACKGROUND OF THE INVENTION

Low density, rigid to semi-rigid polyurethane or polyisocyanurate foamshave utility in a wide variety of insulation applications includingroofing systems, building panels, building envelope insulation, sprayapplied foams, one and two component froth foams, insulation forrefrigerators and freezers, and so called integral skin for applicationsuch as steering wheels and other automotive or aerospace cabin parts,shoe soles, and amusement park restraints. Critical to the large-scalecommercial acceptance of rigid polyurethane foams is their ability toprovide a good balance of properties. For example, rigid polyurethaneand polyisocyanurate foams are known to provide outstanding thermalinsulation, excellent fire resistance properties, and superiorstructural properties at reasonably low densities. Integral skin foamsare known to produce a tough durable outer skin and a cellular,cushioning core.

It is known in the art to produce rigid or semi-rigid polyurethane andpolyisocyanurate foams by reacting a polyisocyanate with one or morepolyols in the presence of one or more blowing agents, one or morecatalysts, one or more surfactants and optionally other ingredients.Blowing agents include hydrocarbons, fluorocarbons, chlorocarbons,chlorofluorocarbons, hydrochlorofluorocarbons, halogenated hydrocarbons,ethers, esters, aldehydes, alcohols, ketones, organic acid or gas, mostoften CO₂, generating materials. Heat is generated when thepolyisocyanate reacts with the polyol, and volatilizes the blowing agentcontained in the liquid mixture, thereby forming bubbles therein. In thecase of gas generating materials, gaseous species are generated bythermal decomposition or reaction with one or more of the ingredientsused to produce the polyurethane or polyisocyanurate foam. As thepolymerization reaction proceeds, the liquid mixture becomes a cellularsolid, entrapping the blowing agent in the foam's cells. If a surfactantis not used in the foaming composition, the bubbles simply pass throughthe liquid mixture without forming a foam or forming a foam with large,irregular cells rendering it not useful.

The foam industry has historically used liquid fluorocarbon blowingagents because of their ease of use and ability to produce foams withsuperior mechanical and thermal insulation properties. Fluorocarbons notonly act as blowing agents by virtue of their volatility, but also areencapsulated or entrained in the closed cell structure of the rigid foamand are the major contributor to the low thermal conductivity propertiesof the rigid urethane foams. Fluorocarbon-based blowing agents alsoproduce a foam having a favorable k-factor. The k-factor is the rate oftransfer of heat energy by conduction through one square foot ofone-inch thick homogenous material in one hour where there is adifference of one degree Fahrenheit perpendicularly across the twosurfaces of the material. Since the utility of closed-cellpolyurethane-type foams is based, in part, on their thermal insulationproperties, it would be advantageous to identify materials that producelower k-factor foams.

Preferred blowing agents also have low global warming potential. Amongthese are hydrohaloolefins including hydrofluoroolefins of whichtrans-1,3,3,3-tetrafluoropropene (1234ze(E)) and1,1,1,4,4,4hexafluorobut-2-ene (1336mzzm(Z)) are of particular interestand hydrochlorofluoroolefins of whichtrans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) is of particularinterest. Processes for the manufacture oftrans-1,3,3,3-tetrafluoropropene are disclosed in U.S. Pat. Nos.7,230,146 and 7,189,884. Processes for the manufacture oftrans-1-chloro-3,3,3-trifluoropropene are disclosed in U.S. Pat. Nos.6,844,475 and 6,403,847.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Thepolyisocyanate and optionally isocyanate compatible raw materials,including but not limited to certain blowing agents and non-reactivesurfactants, comprise the first component, commonly referred to as the“A” component. A polyol or mixture of polyols, one or more surfactant,one or more catalyst, one or more blowing agent, and other optionalcomponents including but not limited to flame retardants, colorants,compatibilizers, and solubilizers comprise the second component,commonly referred to as the “B” component. Accordingly, polyurethane orpolyisocyanurate foams are readily prepared by bringing together the Aand B side components either by hand mix for small preparations and,preferably, machine mix techniques to form blocks, slabs, laminates,pour-in-place panels and other items, spray applied foams, froths, andthe like. Optionally, other ingredients such as fire retardants,colorants, auxiliary blowing agents, and other polyols can be added tothe mixing head or reaction site. Most conveniently, however, they areall incorporated into one B component.

Applicants have come to appreciate that a shortcoming of two-componentsystems, especially those using certain hydrohaloolefins, including1234ze(E), 1336(Z), and 1233zd(E), is the shelf-life of the B-sidecomposition. Normally when a foam is produced by bringing together the Aand B side components, a good foam is obtained. However, applicants havefound that if the polyol premix composition containing a halogenatedolefin blowing agent and a typical amine-containing catalyst is aged,prior to treatment with the polyisocyanate, deleterious effects canoccur. For example, applicants have found that such formulations canproduce a foamable composition which has an undesirable increase inreactivity time and/or a subsequent cell coalescence. The resultingfoams are of lower quality and/or may even collapse during the formationof the foam.

SUMMARY

It has now been found that one source of the problem observerd byapplicants is the reaction of certain amine catalysts with certainhydrohaloolefins. Although applicants do not wish to be bound by or toany particular theory, it is believed that such reactions have bothdirect and indirect deleterious effects. For example, the decompositionreaction depletes the availability of the amine catalyst and hence has anegative effect on reaction times and the quality of foam. In addition,the decomposition reaction produces fluorine ions which can have anative of effect on other components in the pre-mixed and/or foamablecomposition and/or foam, including the surfactant included in suchmaterials.

As a result of extensive testing, applicants have come to appreciatethat the negative effects that have been observed can be overcome by acareful and judicious selection of the catalyst system which is used.More specifically, applicants have found that a catalyst system whichuses relatively little, and preferably contains no substantial amount ofamine catalysts and a relatively high percentage, and substantiallyconsists essentially of metallic catalyst (e.g. inorgano-metalliccatalysts, organo-metallic catalysts) and/or one or more optionalquaternary ammonium carboxylate catalysts.

In addition, while applicants believe that all halogenated olefinblowing agents will exhibit some level of the deleterious effectsmentioned above, applicants had surprisingly and unexpectedly found thata certain halogenated olefin, particularly monochloro-trifluoropropenesand even more particularly trans-1-chloro-3,3,3-trifluoropropene(1233zd(E)), tend to exhibit only a relatively low level of thedeleterious effect, especially when used in combination with catalystwhich contains a relatively low level, and preferably no substantialamount of amine-containing catalyst.

Thus, according to one aspect of the invention, applicants have foundthat blowing agents, foamable compositions, pre-mixes and foams whichutilize metal catalysts (and/or the optional carboxylate catalysts),either alone or in combination with a relatively small amount of aminecatalyst, can extend the shelf life of polyol premixes containinghydrohaloolefins. This advantage is believed to be present withhydrohaloolefins generally, more preferably but not limited to1234ze(E), 1233zd(E), and/or 1336mzzm(Z), and even more preferably with1233zd(E). Applicants have found that good quality foams can be producedaccording to the present invention even if the polyol blend has beenaged several weeks or months.

One aspect of the invention therefore relates to foaming catalystscomprising one or more metal catalysts and optionally amine catalyst,preferably in minor proportion, of a type and in an amount effective topreferably provide little to no loss of reactivity and/or cell structure(ie, shelf life) over time (preferably at least about two (2) months)when combined with hydrohaloolefin blowing agent, preferably 1234ze(E),1233zd(E), and/or 1336mzzm(Z), while achieving a reactivity profilesimilar to a typical amine based catalyst system blowing agents, and toblowing agent compositions, pre-mix compositions, foamable compositionsand foams containing or made from the catalyst.

According to one aspect, this invention relates to rigid to semi-rigid,polyurethane and polyisocyanurate foams and methods for theirpreparation, which foams are characterized by a fine uniform cellstructure and little or no foam collapse. The foams are produced with anorganic polyisocyanate and a polyol premix composition which comprises acombination of a blowing agent, which is preferably a hydrohaloolefin, apolyol, a silicone surfactant, and a catalyst in which catalystcomprises one or more non-amine catalyst, preferably an inorgano- ororgano-metallic compound and/or a carboxylate catalyst, preferably aquaternary ammonium carboxylate catalyst, and also may include one ormore amine catalysts, preferably in a minor proportion based on all thecatalysts in the system.

BRIEF DESCRIPTION ON OF THE DRAWINGS

FIG. 1 is a graphical representation of the results according to thedescription in Example 1.

FIG. 2 is a graphical representation of the results according to thedescription in Example 2.

FIG. 3 is a graphical representation of the results according to thedescription in Example 3.

DETAILED DESCRIPTION OF THE INVENTION:

Although applicants do not intend to be bound by or to any particulartheory of operation, it is believed that the deleterious effectsobserved by applicants may be occurring as a result of the reactionbetween the hydrohaloolefin blowing agent and the amine catalysts toproduce a fluoride ion, which leads to a decrease in the reactivity ofthe blowing agent. In addition, applicants believe that the deleteriouseffects may also be caused, either alone or in addition to the abovecause, by the fluoride ion produced from the above noted reaction inturn reacting with silicone surfactant present in such blowing agentsand related systems to produce a lower average molecular weightsurfactant, which is then a less effective than originally intended.This depletion/degradation of the surfactant tends to reduce theintegrity of the cell wall and hence tends to produce a foam that issubject higher than desired levels of cell collapse.

The invention provides polyol premix composition which comprises acombination of a blowing agent, one or more polyols, one or moresilicone surfactants, and a catalyst in which catalyst is a non-aminecatalyst, such as an inorgano- or organo-metallic compound or quaternaryammonium carboxylate material used either alone or in combination withamine catalysts, wherein the blowing agent comprises one or morehydrohaloolefins, and optionally a hydrocarbon, fluorocarbon,chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenatedhydrocarbon, ether, ester, alcohol, aldehyde, ketone, organic acid, gasgenerating material, water or combinations thereof.

The invention also provides a method of preparing a polyurethane orpolyisocyanurate foam comprising reacting an organic polyisocyanate withthe polyol premix composition.

The Hydrohaloolefin Blowing Agent

The blowing agent component comprises a hydrohaloolefin, preferablycomprising at least one or a combination of 1234ze(E), 1233zd(E), and/or1336mzzm(Z), and optionally a hydrocarbon, fluorocarbon, chlorocarbon,fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether,ester, alcohol, aldehyde, ketone, organic acid, gas generating material,water or combinations thereof.

The hydrohaloolefin preferably comprises at least one halooalkene suchas a fluoroalkene or chlorofluoroalkene containing from 3 to 4 carbonatoms and at least one carbon- carbon double bond. Preferredhydrohaloolefins non-exclusively include trifluoropropenes,tetrafluoropropenes such as (1234), pentafluoropropenes such as (1225),chlorotrifloropropenes such as (1233), chlorodifluoropropenes,chlorotrifluoropropenes, chlorotetrafluoropropenes, hexafluorobutenes(1336) and combinations of these. More preferred for the compounds ofthe present invention are the tetrafluoropropene, pentafluoropropene,and chlorotrifloropropene compounds in which the unsaturated terminalcarbon has not more than one F or Cl substituent. Included are1,3,3,3-tetrafluoropropene (1234ze); 1,1,3,3-tetrafluoropropene;1,2,3,3,3-pentafluoropropene (1225ye), 1,1,1-trifluoropropene;1,2,3,3,3-pentafluoropropene, 1,1,1,3,3-pentafluoropropene (1225zc) and1,1,2,3,3-pentafluoropropene (1225yc); (Z)-1,1,1,2,3-pentafluoropropene(1225yez); 1-chloro-3,3,3-trifluoropropene (1233zd),1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm) or combinations thereof, andany and all stereoisomers of each of these.

Preferred hydrohaloolefins have a Global Warming Potential (GWP) of notgreater than 150, more preferably not greater than 100 and even morepreferably not greater than 75. As used herein, “GWP” is measuredrelative to that of carbon dioxide and over a 100-year time horizon, asdefined in “The Scientific Assessment of Ozone Depletion, 2002, a reportof the World Meteorological Association's Global Ozone Research andMonitoring Project,” which is incorporated herein by reference.Preferred hydrohaloolefins also preferably have an Ozone DepletionPotential (ODP) of not greater than 0.05, more preferably not greaterthan 0.02 and even more preferably about zero. As used herein, “ODP” isas defined in “The Scientific Assessment of Ozone Depletion, 2002, Areport of the World Meteorological Association's Global Ozone Researchand Monitoring Project,” which is incorporated herein by reference.

Coblowing Agents

Preferred optional co-blowing agents non-exclusively include water,organic acids that produce CO₂ and/or CO, hydrocarbons; ethers,halogenated ethers; esters, alcohols, aldehydes, ketones,pentafluorobutane; pentafluoropropane; hexafluoropropane;heptafluoropropane; trans-1,2 dichloroethylene; methylal, methylformate; 1-chloro-1,2,2,2-tetrafluoroethane (124);1,1-dichloro-1-fluoroethane (141b); 1,1,1,2-tetrafluoroethane (134a);1,1,2,2-tetrafluoroethane (134); 1-chloro 1,1-difluoroethane (142b);1,1,1,3,3-pentafluorobutane (365mfc); 1,1,1,2,3,3,3-heptafluoropropane(227ea); trichlorofluoromethane (11); dichlorodifluoromethane (12);dichlorofluoromethane (22); 1,1,1,3,3,3-hexafluoropropane (236fa);1,1,1,2,3,3-hexafluoropropane (236ea); 1,1,1,2,3,3,3-heptafluoropropane(227ea), difluoromethane (32); 1,1-difluoroethane (152a);1,1,1,3,3-pentafluoropropane (245fa); butane; isobutane; normal pentane;isopentane; cyclopentane, or combinations thereof. In certainembodiments the co-blowing agent(s) include one or a combination ofwater and/or normal pentane, isopentane or cyclopentane, which may beprovided with one or a combination of the hydrohaloolefin blowing agentsdiscussed herein.. The blowing agent component is usually present in thepolyol premix composition in an amount of from about 1 wt. % to about 30wt. %, preferably from about 3 wt. % to about 25 wt. %, and morepreferably from about 5 wt. % to about 25 wt. %, by weight of the polyolpremix composition. When both a hydrohaloolefin and an optional blowingagent are present, the hydrohaloolefin component is usually present inthe blowing agent component in an amount of from about 5 wt. % to about90 wt. %, preferably from about 7 wt. % to about 80 wt. %, and morepreferably from about 10 wt. % to about 70 wt. %, by weight of theblowing agent component; and the optional blowing agent is usuallypresent in the blowing agent component in an amount of from about 95 wt.% to about 10 wt. %, preferably from about 93 wt. % to about 20 wt. %,and more preferably from about 90 wt. % to about 30 wt. %, by weight ofthe blowing agent component.

Polyol Component

The polyol component, which includes mixtures of polyols, can be anypolyol which reacts in a known fashion with an isocyanate in preparing apolyurethane or polyisocyanurate foam. Useful polyols comprise one ormore of a sucrose containing polyol; phenol, a phenol formaldehydecontaining polyol; a glucose containing polyol; a sorbitol containingpolyol; a methylglucoside containing polyol; an aromatic polyesterpolyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol;graft copolymers of polyether polyols with a vinyl polymer; a copolymerof a polyether polyol with a polyurea; one or more of (a) condensed withone or more of (b), wherein (a) is selected from glycerine, ethyleneglycol, diethylene glycol, trimethylolpropane, ethylene diamine,pentaerythritol, soy oil, lecithin, tall oil, palm oil, and castor oil;and (b) is selected from ethylene oxide, propylene oxide, a mixture ofethylene oxide and propylene oxide; and combinations thereof. The polyolcomponent is usually present in the polyol premix composition in anamount of from about 60 wt. % to about 95 wt. %, preferably from about65 wt. % to about 95 wt. %, and more preferably from about 70 wt. % toabout 90 wt. %, by weight of the polyol premix composition.

Surfactant

The polyol premix composition next contains a silicone surfactant. Thesilicone surfactant is used to form a foam from the mixture, as well asto control the size of the bubbles of the foam so that a foam of adesired cell structure is obtained. Preferably, a foam with smallbubbles or cells therein of uniform size is desired since it has themost desirable physical properties such as compressive strength andthermal conductivity. Also, it is critical to have a foam with stablecells which do not collapse prior to forming or during foam rise.

Silicone surfactants for use in the preparation of polyurethane orpolyisocyanurate foams are available under a number of trade names knownto those skilled in this art. Such materials have been found to beapplicable over a wide range of formulations allowing uniform cellformation and maximum gas entrapment to achieve very low density foamstructures. The preferred silicone surfactant comprises a polysiloxanepolyoxyalkylene block co-polymer. Some representative siliconesurfactants useful for this invention are Momentive's L-5130, L-5180,L-5340, L-5440, L-6100, L-6900, L-6980 and L-6988; Air Products DC-193,DC-197, DC-5582 , and DC-5598; and B-8404, B-8407, B-8409 and B-8462from Evonik Industries AG of Essen, Germany. Others are disclosed inU.S. Pat. Nos. 2,834,748; 2,917,480; 2,846,458 and 4,147,847. Thesilicone surfactant component is usually present in the polyol premixcomposition in an amount of from about 0.5 wt. % to about 5.0 wt. %,preferably from about 1.0 wt. % to about 4.0 wt. %, and more preferablyfrom about 1.5 wt. % to about 3.0 wt. %, by weight of the polyol premixcomposition.

The polyol premix composition may optionally contain a non-siliconesurfactant, such as a non-silicone, non-ionic surfactant. Such mayinclude oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffinoils, castor oil esters, ricinoleic acid esters, turkey red oil,groundnut oil, paraffins, and fatty alcohols. A preferred non-siliconenon-ionic surfactant is LK-443 which is commercially available from AirProducts Corporation. When a non-silicone, non-ionic surfactant used, itis usually present in the polyol premix composition in an amount of fromabout 0.25 wt. % to about 3.0 wt. %, preferably from about 0.5 wt. % toabout 2.5 wt. %, and more preferably from about 0.75 wt. % to about 2.0wt. %, by weight of the polyol premix composition.

The Catalyst System

Applicants have generally found that it is difficult to identify aminecatalysts which generate relatively low levels of fluoride ions when incontact with hydrohaloolefins while at the same time possessingsufficient activity characteristics to be acceptable for use inproducing foams. In other words, applicants have found that a largenumber of amine catalysts can be identified which are relatively stablewhen in the presence of hydrdohaloolefins, but that such catalysts aregenerally not sufficiently active to provide the necessary foamreactivity. On the other hand, applicants have also found that arelatively large number of amine catalysts can be identified which aresufficiently active to produce acceptable foam reactivity but that suchcatalysts are generally not sufficiently stable for use in combinationwith hydrdohaloolefins, as measured by the generation of fluoride ions.

Based on testing performed by applicants, the following catalysts havebeen found to have the relative fluoride ion generation in the presenceof 1234ze(E) as indicated below in Table 1.

TABLE 1 1234ze(E) CATALYST NO. CATALYST PPM, F-  1 diazabicyclo undecane226,944  2 Diazabicyclooctane (triethylenediamine) 99,000  3Tris-2,4,6-(dimehtylamino-methyl)- 7184phnol/Bis(dimehtylaminomethyl)-phenol  4Dimethylaminoethoxyethanol/ethylene 6020 glycol  5 1-methylimidazole4390  6 polyoxypropylenediamine 3732  7 Pentamethyldiethylene-triamine3242  8 Diethylcyclohexl 1970  9 diethanolamine 1372 10N-mtheyldicyclohexyl-amine 480 11 Methyl(n-methylamino b-sodium acetate458 nonylphenol) 2- 12 Glycerol poly(oxypropylene) triamine 216 13Diisopropylethylamine 67 14 Diethyltoluenediamine 10 151,3,benzenediamine 4-methyl-2,6- 3 bis(mehtylthio)/1,3-benzenediamine 2-methyl-4,6-bis (mehtylthio)

In addition to the above, applicants have tested the reactivity ofseveral of the above-noted catalysts, as measured by Gel Time in secondsin a typical panel foam formulation with the blowing agent consisting of1234ze(E). The results are reported in Tables 2A and 2B provided below:

TABLE 2B GEL TIMES, SEC CATALYSTS (FROM 2.5 14 CHANGE CHART ABOVE)INITIAL DAYS DAYS % PMDETA-Std 78 — — — PMDETA/Acid Block 270 — — —PMDETA/Scavenger 75 88 — +17 DMCHA 140 145 — +3.5 Dicyclohexylmethyl 225280 290 +29 Dicyclohexylmethyl/ 55 65 72 +31 Dibutyltin DilaurateDiisopropylethyl 310 370 375 21

Based upon the testing done by applicants, applicants have found thatfor blowing agents comprising, and preferably consisting essentially of1234ze(E), the catalysts numbered 1-9 in Table 1 above are not generallypreferred because of stability problems, as indicated by the high levelof fluoride concentration. On the other hand, applicants have found thatthe catalysts numbered 12-15, while demonstrating a high level ofstability, are generally not preferred because they are believed to beof not sufficient activity to produce acceptable foam reactivity.Unexpectedly and surprisingly, applicants have found that the catalystsnumbered 10 and 11, namely, n-metheyldicyclohexyl-amine andmethyl(n-methylamino b-sodium acetate nonylphenol) 2- are preferred inaccordance with the present invention because they exhibit a highlydesirable but difficult to achieve combination of stability and activitywhen used in combination with hydrohaloolefins.

Applicants have also surprisingly and unexpectedly found that from amonghydrohaloolefins, 1233zd(E) is substantially less reactive withamine-catalysts in comparison to other hydrohaloolefins, and inparticular hydrohalogenated propenes. More specifically, applicants havefound as a result of testing that the catalysts identified in Table 3below have the relative fluoride ion generation as indicated below inthe presence of 1233zd(E), with foam reactivity performance generallytending from faster to slower as one moves from the top to the bottom ofthe list.

TABLE 3 1233zd(E) CATALYST NO./Tradename CATALYST PPM, F- 1 Polycat DBUDBU 26,994 (estimated) 2. Dabco 33LV Diazabicyclooctane(triethylenediamine) 9900 (estimated) 2A Jeffamine D 230Polyoxypropylenediamine (Jeffamine D 230) 2157 3 Dabco TMR-30Tris-2,4,6-(dimehtylamino-methyl)- 1521phnol/Bis(dimehtylaminomethyl)-phenol 4 Jeffcat ZR 70Dimethylaminoethoxyethanol/ethylene 1753 glycol Toyocat RX5Bis(dimehtylaminoethyl) ether (Toyocat 1002 RX5) Polycat 9Bis(dimehtylaminopropyl)-n (Polycat 9) 754 Polycat 30 Tertiary amine(10-30%), gelling catalyst 548 (30-60%) fatty amine (10-30%) 5 Lupragen1-methyl 1-methylimidazole 221 imidazole 6 polyoxypropylenediamine 19197 Polycat 5 Pentamethyldiethylene-triamine 429 Polycat 41Dimethylaminopropylhexahydrotrivazine, 392 N,N′,N″ 8 Diethylcyclohexl NT9 Dabco DEOA-LF diethanolamine 343 Lupragen 1-methyl 1-methylimidazole221 imidazole Dabco H1010 50/50 blend water + amine salt 171 ToyocatDM70 70% 1,2 dimethylimidazole, 30% 170 ethyleneglycol Toyocat TRXTrimerized catalyst 129 N-Methylmorpholine N-methylmorpholine 102 DIPEADiisopropylethylamine 67 10 Polycat 12 n-methyldicyclohexyl-amine 15 11Curithane 52 Methyl(n-methylamino b-sodium acetate 190 nonylphenol) 2-12 Jeffamine T5000 Glycerol poly(oxypropylene) triamine 49 K-Kat x614Zinc Zinc catalyst complex 36 Jeffcat DMDEE2,2-dimorpholineodiethylether 24 Polycat 12 N-methyldicycohexyl-amine15-22 Firstcure N,N- N,N-dimethylparatoluuidine 20 DimethylparatoluidineEthacure 300 Curative 3,5-dimethythio-2, 4-toluenediamine  9-16 Tyzor TETitanium Titanium complex 10 Dabco MB20 Bismuth carboxylate catalyst 6Borchi Oxycoat 1101 Iron catalyst 2 PUCAT 25 Bismuth 2-ethylhexzanoate(25%) 1 13 Diisopropylethylamine NT 14 Ethacure 100 curingDiethyltoluenediamine 24 agent 15 Ethacure 300 Curative1,3,benzenediamine 4-methyl-2,6- 16 bis(mehtylthio)/1,3-benzenediamine2- methyl-4,6-bis (mehtylthio) NT—not tested

As can be seen from the results reported above, applicants have foundthat 1233zd(E) is many times more stable, as measured by fluoride iongeneration, in the presence of amine catalysts than are otherhalogenated olefins, and particularly halogenated propenes. Moreover, aneven more unexpectedly, applicants have found that 1-methylimidazoleexhibits an exceptionally high level of stability while retaining arelatively high level of foam reactivity when used in combination with1233zd(E). Similarly, applicants have unexpectedly found thatn-methyldicyclohexyl-amine exhibits an exceptionally high level ofstability while retaining a relatively high level of foam reactivitywhen used in combination with 1233zd(E).

Notwithstanding the unexpected and advantageous results described aboveregarding combinations of halogenated olefins and certain aminecatalysts, applicants have found that even the best of such combinationsis not fully satisfactory for many embodiments, and that furthersubstantial and unexpected improvement can be achieved by replacing allor a substantial portion of the amine catalyst(s) with one or more metalcatalysts, and even more preferably two or more catalysts wherein atleast a first and a second of said catalysts is based upon a differentmetal. In general, applicants have found that metal catalysts arerelatively nonreactive with halogenated olefins that are adaptable foruse as blowing agents and therefore appear to produce a relativelystable system, and that with a judicious selection of at least a firstand second metal catalyst surprisingly effective and stablecompositions, systems and methods can be obtained.

Applicants have found that the use of a catalyst system based upon asingle metal in many embodiments is not capable of fully satisfying thedesired reactivity profile for the foamable composition and/or method.Applicants have found that surprising and highly beneficial results canbe achieved by the selection of catalyst systems comprising a firstmetal catalyst wherein said first metal is selected from a metalcatalysts exhibiting relatively high activity at low temperatures and asecond metal catalyst wherein said second metal is selected from thecatalytic metals tending to exhibit relatively high activity at highertemperatures. In certain preferred embodiments, the metal of the firstmetal catalyst is selected from the group consisting of kin, zinc,cobalt, lead and combinations of these. In certain preferredembodiments, the metal of the second metal catalyst is selected from thegroup consisting of bismuth, sodium, calcium and combinations of these.In highly preferred embodiments of the present invention, the catalystsystem comprises a first metal catalyst and a second metal catalyst butis substantially free of amine catalyst.

Furthermore, applicants have found that blowing agents and foamablesystems that are highly desirable in certain embodiments can be obtainedby utilizing one or more of the preferred amine catalysts of the presentinvention in combination with at least one, and preferably at least two,metal catalysts according to the invention as described above.

In certain embodiments, the non-amine catalysts are inorgano- ororgano-metallic compounds. Useful inorgano- or organo-metallic compoundsinclude, but are not limited to, organic salts, Lewis acid halides, orthe like, of any metal, including, but not limited to, transitionmetals, post-transition (poor) metals, rare earth metals (e.g.lanthanides), metalloids, alkali metals, alkaline earth metals, or thelike. According to certain broad aspects of the present invention, themetals may include, but are not limited to, bismuth, lead, tin, zinc,chromium, cobalt, copper, iron, manganese, magnesium, potassium, sodium,titanium, mercury, zinc, antimony, uranium, cadmium, thorium, aluminum,nickel, cerium, molybdenum, vanadium, zirconium, or combinationsthereof. Non-exclusive examples of such inorgano- or organo-metalliccatalysts include, but are not limited to, bismuth nitrate, lead2-ethylhexoate, lead benzoate, lead naphthanate, ferric chloride,antimony trichloride, antimony glycolate, tin salts of carboxylic acids,dialkyl tin salts of carboxylic acids, potassium acetate, potassiumoctoate, potassium 2-ethylhexoate, potassium salts of carboxylic acids,zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts,alkali metal carboxylic acid salts, sodiumN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate, tin (II)2-ethylhexanoate, dibutyltin dilaurate, or combinations thereof. Incertain preferred embodiments the catalysts are present in the polyolpremix composition in an amount of from about 0.001 wt. % to about 5.0wt. %, 0.01 wt. % to about 3.0 wt. %, preferably from about 0.3 wt. % toabout 2.5 wt. %, and more preferably from about 0.35 wt. % to about 2.0wt. %, by weight of the polyol premix composition. While these are usualamounts, the quantity amount of the foregoing catalyst can vary widely,and the appropriate amount can be easily be determined by those skilledin the art.

Furthermore, applicants have found that it is desirable to use certainmetal catalysts in foamable and foaming systems having relatively highlevels of water. More specifically, applicants have found that catalystsbased on tin and potassium are preferred in such systems because oftheir ability to retain their reactivity and avoid stability problems insuch high water systems. Furthermore, applicants have found thatcatalysts based upon zinc and bismuth have a tendency to precipitate outof the formulation, especially in systems having relatively high watercontent, although such catalysts have desirable performance profiles tothe extent precipitation can be avoided. For this reason, it ispreferred in certain systems that the metal catalysts comprise at leasta first catalysts based upon tin and/or zinc, and a second catalystbased upon potassium and/or bismuth.

In another embodiment of the invention, the non-amine catalyst is aquaternary ammonium carboxylate. Useful quaternary ammonium carboxylatesinclude, but are not limited to: (2-hydroxypropyl)trimethylammonium2-ethylhexanoate (TMR® sold by Air Products and Chemicals) and(2-hydroxypropyl)trimethylammonium formate (TMR-2® sold by Air Productsand Chemicals). These quaternary ammonium carboxylate catalysts areusually present in the polyol premix composition in an amount of fromabout 0.25 wt. % to about 3.0 wt. %, preferably from about 0.3 wt. % toabout 2.5 wt. %, and more preferably from about 0.35 wt. % to about 2.0wt. %, by weight of the polyol premix composition. While these are usualamounts, the quantity amount of catalyst can vary widely, and theappropriate amount can be easily be determined by those skilled in theart.

In another embodiment, as mentioned above, the non-amine catalyst isused in combination with an amine catalyst. Such amine catalysts mayinclude any compound containing an amino group and exhibiting thecatalytic activity provided herein. Such compounds may be straight chainor cyclic non-aromatic or aromatic in nature. Useful, non-limiting,amines include primary amines, secondary amines or tertiary amines.Useful tertiary amine catalysts non-exclusively includeN,N,N′,N″,N″-pentamethyldiethyltriamine, N,N-dicyclohexylmethyl amine;N,N-ethyldiisopropylamine; N,N-dimethylcyclohexylamine;N,N-dimethylisopropylamine; N-methyl-N-isopropylbenzylamine;N-methyl-N-cyclopentylbenzylamine;N-isopropyl-N-sec-butyl-trifluoroethylamine;N,N-diethyl-(α-phenylethyl)amine, N,N,N-tri-n-propylamine, orcombinations thereof. Useful secondary amine catalysts non-exclusivelyinclude dicyclohexylamine; t-butylisopropylamine; di-t-butylamine;cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine;di-(α-trifluoromethylethyl)amine; di-(α-phenylethyl)amine; orcombinations thereof. Useful primary amine catalysts non-exclusivelyinclude: triphenylmethylamine and 1,1-diethyl-n-propylamine.

Other useful amines includes morpholines, imidazoles, ether containingcompounds, and the like. These include:

-   dimorpholinodiethylether-   N-ethylmorpholine-   N-methylmorpholine-   bis(dimethylaminoethyl) ether-   imidizole-   n-methylimidazole-   1,2-dimethylimidazole-   dimorpholinodimethylether-   N,N,N′,N′,N″,N″-pentamethyldiethylenetriamine-   N,N,N′,N′,N″,N″-pentaethyldiethylenetriamine-   N,N,N′,N′,N″,N″-pentamethyldipropylenetriamine-   bis(diethylaminoethyl) ether-   bis(dimethylaminopropyl) ether.

In embodiments where an amine catalyst is provided, the catalyst may beprovided in any amount to achieve the function of the instant inventionwithout affecting the foam forming or storage stability of thecomposition, as characterized herein. To this end, the amine catalystmay be provided in amounts less than or greater than the non-aminecatalyst.

The preparation of polyurethane or polyisocyanurate foams using thecompositions described herein may follow any of the methods well knownin the art can be employed, see Saunders and Frisch, Volumes I and IIPolyurethanes Chemistry and technology, 1962, John Wiley and Sons, NewYork, N.Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, OxfordUniversity Press, New York, N.Y. or Klempner and Sendijarevic, PolymericFoams and Foam Technology, 2004, Hanser Gardner Publications,Cincinnati, Ohio. In general, polyurethane or polyisocyanurate foams areprepared by combining an isocyanate, the polyol premix composition, andother materials such as optional flame retardants, colorants, or otheradditives. These foams can be rigid, flexible, or semi-rigid, and canhave a closed cell structure, an open cell structure or a mixture ofopen and closed cells.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally other isocyanate compatible raw materials,including but not limited to blowing agents and certain siliconesurfactants, comprise the first component, commonly referred to as the“A” component. The polyol mixture composition, including surfactant,catalysts, blowing agents, and optional other ingredients comprise thesecond component, commonly referred to as the “B” component. In anygiven application, the “B” component may not contain all the abovelisted components, for example some formulations omit the flameretardant if flame retardancy is not a required foam property.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, water, and evenother polyols can be added as a stream to the mix head or reaction site.Most conveniently, however, they are all incorporated into one Bcomponent as described above.

A foamable composition suitable for forming a polyurethane orpolyisocyanurate foam may be formed by reacting an organicpolyisocyanate and the polyol premix composition described above. Anyorganic polyisocyanate can be employed in polyurethane orpolyisocyanurate foam synthesis inclusive of aliphatic and aromaticpolyisocyanates. Suitable organic polyisocyanates include aliphatic,cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanateswhich are well known in the field of polyurethane chemistry. These aredescribed in, for example, U.S. Pat. Nos. 4,868,224; 3,401,190;3,454,606; 3,277,138; 3,492,330; 3,001,973; 3,394,164; 3,124.605; and3,201,372. Preferred as a class are the aromatic polyisocyanates.

Representative organic polyisocyanates correspond to the formula:

R(NCO)z

wherein R is a polyvalent organic radical which is either aliphatic,aralkyl, aromatic or mixtures thereof, and z is an integer whichcorresponds to the valence of R and is at least two. Representative ofthe organic polyisocyanates contemplated herein includes, for example,the aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluenediisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crudetoluene diisocyanate, methylene diphenyl diisocyanate, crude methylenediphenyl diisocyanate and the like; the aromatic triisocyanates such as4,4′,4″-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates;the aromatic tetraisocyanates such as4,4′-dimethyldiphenylmethane-2,2′5,5-″tetraisocyanate, and the like;arylalkyl polyisocyanates such as xylylene diisocyanate; aliphaticpolyisocyanate such as hexamethylene-1,6-diisocyanate, lysinediisocyanate methylester and the like; and mixtures thereof. Otherorganic polyisocyanates include polymethylene polyphenylisocyanate,hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate,naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate,4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenyldiisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, and3,3′-dimethyldiphenylmethane-4,4′-diisocyanate; Typical aliphaticpolyisocyanates are alkylene diisocyanates such as trimethylenediisocyanate, tetramethylene diisocyanate, and hexamethylenediisocyanate, isophorene diisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), and the like; typical aromatic polyisocyanates include m-,and p-phenylene disocyanate, polymethylene polyphenyl isocyanate, 2,4-and 2,6-toluenediisocyanate, dianisidine diisocyanate, bitoyleneisocyanate, naphthylene 1,4-diisocyanate,bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane,and the like. Preferred polyisocyanates are the polymethylene polyphenylisocyanates, Particularly the mixtures containing from about 30 to about85 percent by weight of methylenebis(phenyl isocyanate) with theremainder of the mixture comprising the polymethylene polyphenylpolyisocyanates of functionality higher than 2. These polyisocyanatesare prepared by conventional methods known in the art. In the presentinvention, the polyisocyanate and the polyol are employed in amountswhich will yield an NCO/OH stoichiometric ratio in a range of from about0.9 to about 5.0. In the present invention, the NCO/OH equivalent ratiois, preferably, about 1.0 or more and about 3.0 or less, with the idealrange being from about 1.1 to about 2.5. Especially suitable organicpolyisocyanate include polymethylene polyphenyl isocyanate,methylenebis(phenyl isocyanate), toluene diisocyanates, or combinationsthereof.

In the preparation of polyisocyanurate foams, trimerization catalystsare used for the purpose of converting the blends in conjunction withexcess A component to polyisocyanurate-polyurethane foams. Thetrimerization catalysts employed can be any catalyst known to oneskilled in the art, including, but not limited to, glycine salts,tertiary amine trimerization catalysts, quaternary ammoniumcarboxylates, and alkali metal carboxylic acid salts and mixtures of thevarious types of catalysts. Preferred species within the classes arepotassium acetate, potassium octoate, and sodiumN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Conventional flame retardants can also be incorporated, preferably inamount of not more than about 20 percent by weight of the reactants.Optional flame retardants include tris(2-chloroethyl)phosphate,tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate,tris(1,3-dichloropropyl)phosphate, tri(2-chloroisopropyl)phosphate,tricresyl phosphate, tri(2,2-dichloroisopropyl)phosphate, diethylN,N-bis(2-hydroxyethyl) aminomethylphosphonate, dimethylmethylphosphonate, tri(2,3-dibromopropyl)phosphate,tri(1,3-dichloropropyl)phosphate, and tetra-kis-(2-chloroethyl)ethylenediphosphate, triethylphosphate, diammonium phosphate, varioushalogenated aromatic compounds, antimony oxide, aluminum trihydrate,polyvinyl chloride, melamine, and the like. Other optional ingredientscan include from 0 to about 7 percent water, which chemically reactswith the isocyanate to produce carbon dioxide. This carbon dioxide actsas an auxiliary blowing agent. Formic acid is also used to producecarbon dioxide by reacting with the isocyanate and is optionally addedto the “B” component.

In addition to the previously described ingredients, other ingredientssuch as, dyes, fillers, pigments and the like can be included in thepreparation of the foams. Dispersing agents and cell stabilizers can beincorporated into the present blends. Conventional fillers for useherein include, for example, aluminum silicate, calcium silicate,magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate,glass fibers, carbon black and silica. The filler, if used, is normallypresent in an amount by weight ranging from about 5 parts to 100 partsper 100 parts of polyol. A pigment which can be used herein can be anyconventional pigment such as titanium dioxide, zinc oxide, iron oxide,antimony oxide, chrome green, chrome yellow, iron blue siennas,molybdate oranges and organic pigments such as para reds, benzidineyellow, toluidine red, toners and phthalocyanines.

The polyurethane or polyisocyanurate foams produced can vary in densityfrom about 0.5 pounds per cubic foot to about 60 pounds per cubic foot,preferably from about 1.0 to 20.0 pounds per cubic foot, and mostpreferably from about 1.5 to 6.0 pounds per cubic foot. The densityobtained is a function of how much of the blowing agent or blowing agentmixture disclosed in this invention plus the amount of auxiliary blowingagent, such as water or other co-blowing agents is present in the A and/ or B components, or alternatively added at the time the foam isprepared. These foams can be rigid, flexible, or semi-rigid foams, andcan have a closed cell structure, an open cell structure or a mixture ofopen and closed cells. These foams are used in a variety of well knownapplications, including but not limited to thermal insulation,cushioning, flotation, packaging, adhesives, void filling, crafts anddecorative, and shock absorption.

The following non-limiting examples serve to illustrate the invention.

EXAMPLE 1 Spray Foanm

Two typical commercial polyol spray-foam formulations are formed inaccordance with Table E1A below:

TABLE E1A Polyol Blend, 50° F. (10° C.) 245fa 1233zd(E) Components phpphp Mannich polyether polyol having an OH# 470 40 40 (Veranol 470X)Aromatic polyester polyol (Terate 4020) 60 60 Silicone surfactant (DabcoDC193) 2.0 2.0 Potassium octoate solution-15% in diethylene 1.4 1.4glycol (Dabco K-15) Polycat 5 (pentamethyldiethylene-triamine) 1.4 1.4Dabco 33LV (Diazabicyclooctane 0.7 0.7 (triethylenediamine) TCPP (tris(2-chloroisopropyl) phosphate 20 20 (Antiblaze TMCP(AB80)) Water 2 2245fa 20 0 1233zd(E) 0 20 Isocyanate, 70° F. (21° C.)Polymethyldiisocyanate (PMDI) (Lupranate M20S) ISO ISO Index = Index =150 150

The formulations are maintained for up to 168 hours at about 52 C. Threedifferent foams are formed from each formulation: one essentially uponinitial formulation; one after about 62 hours of aging; and one after168 hours of aging. Gel time is observed for each of the foams thusformed and the results are provided in FIG. 1.

As can be seen from the above example and the results illustrated inFIG. 1, the gel time for a typical foam formulation, particularly aspray foam formulation, increases substantially (63% after 62 hours and113% after 168 hours) when the blowing agent consists of 1233zd as thefoamable composition is aged when a typical catalyst formulation isused, especially in comparison to level of increased which is observedfor saturated blowing agent materials such as HFC-245fa. Those skilledin the art would appreciate that such performance is generallyconsidered not acceptable for many commercial embodiments.

EXAMPLE 2 Spray Foam without Catalyst

A typical commercial polyol spray-foam formulations, except with nocatalyst present, is formed in accordance with Table E2 below.

TABLE E2 Polyol Blend, 50° F. (10° C.) Components php Voranol ® 470X 40Terate 4020 ® 60 Dabco ® DC193 2 Water 2 Antiblaze ® AB80 20 1233zd(E)20 Isocyanate, 70° F. (21° C.) Lupranate ® M20S ISO Index = 150After testing for stability, the results are as indicated FIG. 2.

The results reported above and illustrated in FIG. 2 indicate that1233zd(E) is acceptable as a blowing agent for use in combination withtypical commercially used polyol compounds, including particularlypolyol compounds used in typical commercial spray foam applicationswithout catalyst.

EXAMPLE 3A Spray Foam with Catalyst

A polyol spray-foam formulation according to the present invention isformed using the preferred blowing agent 1233zd(E) but with aless-preferred catalyst system consisting of a single bismuth metalcatalyst and a non-preferred amine-based catalyst in accordance withTable E3A below:

TABLE E3A Polyol Blend, 50° F. (10° C.) Components Php Voranol ® 9 470X40.0 (Mannich polyether polyol) Terate ® 10 4020 60.0 (Aromaticpolyester polyol) Dabco ® 1 DC193 2.0 (Silicone surfactant) Dabco K-151.4 Polycat 5 1.4 MB-20 Bismuth Catalyst 0.7 Antiblaze ® 13 AB80 20Water 2 1233zd 20 Isocyanate, 70° F. (21° C.) Lupranate ® 3 M20S IsoIndex = 150

Acceptabe results are obtained.

EXAMPLE 3B Spray Foam with Catalyst

A polyol spray-foam formulation the same as Example 3A is formed usingthe preferred blowing agent 1233zd(E), except the catalyst is replacedwith a more preferred catalyst system of the present inventionconsisting of a first metal (zinc) catalyst and second metal (bismuth)catalyst and a preferred amine-based catalyst in accordance with TableE3B:

TABLE E3B Polyol Blend 50° F. (10° C.) Components Php Voranol ® 9 470X40.0 (Mannich polyether polyol) Terate ® 10 4020 60.0 (Aromaticpolyester polyol) Dabco ® 1 DC193 2.0 (Silicone surfactant) Dabco K-151.4 Polycat 12 2.0 K-Kat ® 11 XK-614 Zinc Catalyst 2.0 MB-20 BismuthCatalyst 0.7 Antiblaze ® 13 AB80 20 Water 2 1233zd(E) 20 Isocyanate, 70°F. (21° C.) Lupranate ® 3 M20S Iso Index = 150

After testing for stability, the results illustrated in FIG. 3 areobtained. As can be seen from the above example and the resultsillustrated in FIG. 3, the gel time for a typical foam formulation,particularly a spray foam formulation, did not increase after 62 hoursand increased only 8% after 168 hours when the blowing agent consists of1233zd and a preferred catalyst of the present invention is used. Thoseskilled in the art would appreciate that such performance is generallyconsidered acceptable for many commercial embodiments and wouldappreciate that such an improvement in gel time performance issubstantial, significant and surprising. In FIG. 3, the data representedby the white column and labeled “1233zd(E)” corresponding to the resultsfrom the formulation in Example 2 and the data represented by the greencolumn and labeled “1233zd(E)+modified catalyst” corresponds to theresults from formulation in this Example 3B.

The results reported in this example illustrate the surprising andhighly beneficial advantages associated with use of blowing agents,foamable compositions, foams and foaming methods using the preferredcatalysts of the present invention.

EXAMPLE 3C Spray Foam with Catalyst

A polyol spray-foam formulation different than the formulation used inExample 3A is formed using the preferred blowing agent 1233zd(E) asreported in Table E3C below.

TABLE E3C Polyol Blend 40° F. (4.4° C.) Components Php Polyether polyolEDA-PO, 70 EDA-PO/EO (50/50) Mannich polyol (OH 350) 30.0 Dabco ® 1DC193 1.5 (Silicone surfactant) Lead (20%) 0.5 Dabco K-15 1.5 Polycat 122.0 K-Kat ® 11 XK-614 Zinc Catalyst 2.0 K-Kat XK-227 Bismuth Catalyst0.7 Antiblaze ® 13 AB80 20 Water 1.5 1233zd(E) 30 Isocyanate, 70° F.(21° C.) Lupranate ® 3 M20S Iso Index = 150

As can be seen from the table above, the type and amounts of the variouscomponents are changed, but a catalyst consisting of a first metal(zinc) catalyst and second metal (bismuth) catalyst and a preferredamine-based catalyst is used.

The gel time for this typical foam formulation, particularly a sprayfoam formulation, did not increase after three months storage at roomtemperature when the blowing agent consists of 1233zd and a preferredcatalyst of the present invention is used as per Table E3A. Thoseskilled in the art would appreciate that such performance is generallyconsidered acceptable for many commercial embodiments and wouldappreciate that such an improvement in gel time performance issubstantial, significant and surprising.

EXAMPLE 4 Comparative Example

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5parts by weight water, 1.2 parts by weight pentamethyldiethylenetriamine(sold as Polycat 5 by Air Products and Chemicals) catalyst, and 8 partsby weight trans-1,3,3,3-tetrafluoropropene blowing agent. The total Bcomponent composition, when freshly prepared and combined with 120.0parts by weight of Lupranate M2OS polymeric isocyanate yielded a goodquality foam with a fine and regular cell structure. Foam reactivity wastypical for a pour in place foam. The total B-side composition (112.2parts) was then aged at 130° F. for 62 hours, and then combined with120.0 parts of M20S polymeric isocyanate to make a foam. The foam wasvery poor in appearance with significant cell collapse. Significantyellowing of the polyol premix was noted during aging.

EXAMPLE 5 Comparative Example

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5parts by weight water, 1.2 parts by weight pentamethyldiethylenetriamine(sold as Polycat 5 by Air Products and Chemicals) catalyst and 8 partsby weight blowing agent trans-1-chloro-3,3,3-trifluoropropene. The totalB component composition, when freshly prepared and combined with 120.0parts by weight of Lupranate M20S polymeric isocyanate yielded a goodquality foam with a fine and regular cell structure. Foam reactivity wastypical for a pour in place foam. The total B-side composition (112.2parts) was then aged at 130° F. for 168 hours, and then combined with120.0 parts of M20S polymeric isocyanate to make a foam. The foam wasvery poor in appearance with significant cell collapse. Significantyellowing of the polyol premix was noted during aging.

EXAMPLE 6 Foam Test

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5parts by weight water, 2.0 parts by weight N,N-dicyclohexylmethylamine(sold as Polycat 12 by Air Products and Chemicals) catalyst, 1.75 partsby weight a bismuth based catalyst (sold as Dabco MB-20 by Air Productsand Chemicals) and 8 parts by weight trans-1,3,3,3-tetrafluoropropeneblowing agent. The total B component composition, when freshly preparedand combined with 120.0 parts by weight of Lupranate M20S polymericisocyanate yielded a good quality foam with a fine and regular cellstructure. Foam reactivity was typical for a pour in place foam. Thetotal B-side composition (114.75 parts) was then aged at 130° F. for 336hours, and then combined with 120.0 parts of M20S polymeric isocyanateto make a foam. The foam was excellent in appearance with no evidence ofcell collapse. There was no yellowing of the polyol premix noted duringaging.

EXAMPLE 7 Foam Test

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 0.5parts by weight water, 2.0 parts by weight N,N-dicyclohexylmethylamine(sold as Polycat 12 by Air Products and Chemicals) catalyst, 1.75 partsby weight of zinc 2-ethylhexanoate (sold as 30-3038 by Strem Chemicals)and 8 parts by weight trans-1-chloro-3,3,3-trifluoropropene blowingagent. The total B component composition, when freshly prepared andcombined with 103.0 parts by weight of Lupranate M20S polymericisocyanate yielded a good quality foam with a fine and regular cellstructure. Foam reactivity was typical for a pour in place foam. Thetotal B-side composition (113.75 parts) was then aged at 130° F. for 336hours, and then combined with 103.0 parts of M20S polymeric isocyanateto make a foam. The foam was excellent in appearance with no evidence ofcell collapse. There was no yellowing of the polyol premix noted duringaging

EXAMPLE 8 Foam Test

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.0parts by weight water, 2.0 parts by weight N,N-dicyclohexylmethylamine(sold as Polycat 12 by Air Products and Chemicals) catalyst, 1.75 partsby weight a Potassium based catalyst (sold as Dabco K15 by Air Productsand Chemicals) and 8 parts by weighttrans-l-chloro-3,3,3-trifluoropropene blowing agent. The total Bcomponent composition, when freshly prepared and combined with 112.0parts by weight of Lupranate M20S polymeric isocyanate yielded a goodquality foam with a fine and regular cell structure. Foam reactivity wastypical for a pour in place foam. The total B-side composition (114.75parts) was then aged at 130 ° F. for 504 hours, and then combined with112.0 parts of M20S polymeric isocyanate to make a foam. The foam wasgood in appearance with only slight evidence of cell collapse. There wasvery slight yellowing of the polyol premix noted during aging.

EXAMPLE 9 Foam Test

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5parts by weight water, 2.0 parts by weight methyl(n-methylamino b-sodiumacetate nonylphenol) 2- catalyst, 1.75 parts by weight a bismuth basedcatalyst (sold as Dabco MB-20 by Air Products and Chemicals) and 8 partsby weight trans-1,3,3,3-tetrafluoropropene blowing agent. The total Bcomponent composition, when freshly prepared and combined with 120.0parts by weight of Lupranate M20S polymeric isocyanate yielded a goodquality foam with a fine and regular cell structure. Foam reactivity wastypical for a pour in place foam. The total B-side composition (114.75parts) was then aged at 130° F. for 336 hours, and then combined with120.0 parts of M20S polymeric isocyanate to make a foam. The foam wasexcellent in appearance with no evidence of cell collapse. There was noyellowing of the polyol premix noted during aging.

EXAMPLE 10 Foam Test

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 0.5parts by weight water, 2.0 parts by weight methyl(n-methylamino b-sodiumacetate nonylphenol) 2-, 1.75 parts by weight of zinc 2-ethylhexanoate(sold as 30-3038 by Strem Chemicals) and 8 parts by weighttrans-1-chloro-3,3,3-trifluoropropene blowing agent. The total Bcomponent composition, when freshly prepared and combined with 103.0parts by weight of Lupranate M20S polymeric isocyanate yielded a goodquality foam with a fine and regular cell structure. Foam reactivity wastypical for a pour in place foam. The total B-side composition (113.75parts) was then aged at 130° F. for 336 hours, and then combined with103.0 parts of M20S polymeric isocyanate to make a foam. The foam wasexcellent in appearance with no evidence of cell collapse. There was noyellowing of the polyol premix noted during aging

EXAMPLE 11 Foam Test

A polyol (B Component) formulation was made up of 100 parts by weight ofa polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.0parts by weight water, 2.0 parts by weight methyl(n-methylamino b-sodiumacetate nonylphenol) 2-, 1.75 parts by weight a Potassium based catalyst(sold as Dabco K15 by Air Products and Chemicals) and 8 parts by weighttrans-1-chloro-3,3,3-trifluoropropene blowing agent. The total Bcomponent composition, when freshly prepared and combined with 112.0parts by weight of Lupranate M20S polymeric isocyanate yielded a goodquality foam with a fine and regular cell structure. Foam reactivity wastypical for a pour in place foam. The total B-side composition (114.75parts) was then aged at 130° F. for 504 hours, and then combined with112.0 parts of M20S polymeric isocyanate to make a foam. The foam wasgood in appearance with only slight evidence of cell collapse. There wasvery slight yellowing of the polyol premix noted during aging.

What is claimed is:
 1. A foamable composition comprising: a. ahydrohaloolefin blowing agent, b. one or more polyols, c. one or moresurfactants, and d. a catalyst system comprising at least a first metaland at least a second metal, and at least one amine catalyst selectedfrom n-metheyldicyclohexyl-amine and methyl(n-methylamino b-sodiumacetate nonylphenol) 2- and combinations of these.
 2. The foamablecomposition of claim 1 wherein said first and second metal catalyst isselected from the group consisting of bismuth nitrate, lead2-ethylhexoate, lead benzoate, lead naphthanate, ferric chloride,antimony trichloride, antimony glycolate, tin salts of carboxylic acids,dialkyl tin salts of carboxylic acids, potassium acetate, potassiumoctoate, potassium 2-ethylhexoate, potassium salts of carboxylic acids,zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts,alkali metal carboxylic acid salts, and sodiumN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate, tin (II)2-ethylhexanoate, dibutyltin dilaurate, and combinations thereof.
 3. Thefoamable composition of claim 2 wherein said first and second metalcatalyst is each present in an amount of about 0.001 wt. % to about 5.0wt. %, by weight of the composition.
 4. The foamable composition ofclaim 1 further comprising a quaternary ammonium carboxylate.
 5. Thefoamable composition of claim 4 wherein said quaternary ammoniumcarboxylate is (2hydroxypropyl)trimethylammonium 2-ethylhexanoate or(2-hydroxypropyl)trimethylammonium formate.
 6. The foamable compositionof claim 5 wherein said quaternary ammonium carboxylate is present in anamount of about 0.25 wt. % to about 3.0 wt. %, by weight of thecomposition.
 7. The foamable composition of claim 1 wherein said blowingagent further comprises a co-blowing agent selected from the groupconsisting of water, hydrocarbon, fluorocarbon, chlorocarbon,hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon,ether, ester, alcohol, aldehyde, ketone, organic acid, gas generatingmaterial, and combinations thereof.
 8. The foamable composition of claim1 wherein said blowing agent comprises 3 to 4 carbon atoms and at leastone carbon-carbon double bond.
 9. The foamable composition of claim 8wherein said blowing agent comprises a hydrohaloolefin selected from thegroup consisting of trifluoropropene, tetrafluoropropene,pentafluoropropane, chlorotrifluoropropene, chlorodifluoropropenes,chlorotrifluoropropene, chlorotetrafluoropropene, hexafluorobutene, andcombinations of these.
 10. The foamable composition of claim 8 whereinsaid blowing agent comprises a hydrohaloolefin selected from the groupconsisting of tetrafluoropropene, pentafluoropropene, andchlorotrifloropropene wherein said hydrohaloolefin comprises anunsaturated terminal carbon having not more than one F or Clsubstituent.
 11. The foamable composition of claim 8 wherein saidblowing agent is selected from the group consisting of1,3,3,3-tetrafluoropropene (1234ze); 1,1,3,3-tetrafluoropropene;1,2,3,3,3-pentafluoropropene (1225ye); 1,1,1-trifluoropropene;1,1,1,3,3-pentafluoropropene (1225zc); 1,1,2,3,3-pentafluoropropene(1225yc); (Z)-1,1,1,2,3-pentafluoropropene (1225yez);1-chloro-3,3,3-trifluoropropene (1233zd); 1,1,1,4,4,4hexafluorobut-2-ene(1336mzzm) and combinations thereof.
 12. The foamable composition ofclaim 8 wherein said blowing agent comprises in substantial proportion1233zd(E).
 13. The foamable composition of claim 1 wherein said aminecatalyst comprises n-metheyldicyclohexyl-amine.
 14. The foamablecomposition of claim 13 wherein the amine catalyst comprisesmethyl(n-methylamino b-sodium acetate nonylphenol) 2-.
 15. A polyolpremix composition comprising: a. a hydrohaloolefin blowing agent, b.one or more polyols, c. one or more surfactants, and d. a non-aminecatalyst selected from the group consisting of an a first metal catalystand a second metal catalyst, wherein the metal of said first metalcatalyst is not the same as the metal of said second catalyst, each ofsaid first and second metal catalysts comprise an organic salt whereinthe metal is selected from the group consisting of bismuth, lead, tin,zinc, chromium, cobalt, copper, iron, manganese, magnesium, potassium,sodium, titanium, mercury, zinc, antimony, uranium, cadmium, thorium,aluminum, nickel, cerium, molybdenum, vanadium, zirconium, andcombinations thereof.
 16. The polyol premix composition of claim 15wherein each of said first and second metal catalysts comprise acompound selected from the group consisting of bismuth nitrate, lead2-ethylhexoate, lead benzoate, lead naphthanate, ferric chloride,antimony trichloride, antimony glycolate, tin salts of carboxylic acids,dialkyl tin salts of carboxylic acids, potassium acetate, potassiumoctoate, potassium 2-ethylhexoate, potassium salts of carboxylic acids,zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts,alkali metal carboxylic acid salts, sodiumN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate, tin (II)2-ethylhexanoate, dibutyltin dilaurate, and combinations thereof. 17.The polyol premix composition of claim 15 wherein said blowing agentcomprises 3 to 4 carbon atoms and at least one carbon-carbon doublebond.
 18. The polyol premix composition of claim 15 wherein said blowingagent comprises a hydrohaloolefin selected from the group consisting oftrifluoropropene, tetrafluoropropene, pentafluoropropane,chlorotrifluoropropene, chlorodifluoropropenes, chlorotrifluoropropene,chlorotetrafluoropropene, hexafluorobutene, and combinations of these.19. The polyol premix composition of claim 15 wherein said blowing agentcomprises a hydrohaloolefin selected from the group consisting oftetrafluoropropene, pentafluoropropene, and chlorotrifloropropenewherein said hydrohaloolefin comprises an unsaturated terminal carbonhaving not more than one F or Cl sub stituent.
 20. The polyol premixcomposition of claim 15 wherein said blowing agent is 1234ze(E),1233zd(E), or 1336mzzm(Z).